CA2271341C - Liquid phase catalytic fluorination of hydrochlorocarbon and hydrochlorofluorocarbon - Google Patents
Liquid phase catalytic fluorination of hydrochlorocarbon and hydrochlorofluorocarbon Download PDFInfo
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- CA2271341C CA2271341C CA002271341A CA2271341A CA2271341C CA 2271341 C CA2271341 C CA 2271341C CA 002271341 A CA002271341 A CA 002271341A CA 2271341 A CA2271341 A CA 2271341A CA 2271341 C CA2271341 C CA 2271341C
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- halide
- formula
- pentavalent
- mixture
- hydrochlorocarbon
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- 238000003682 fluorination reaction Methods 0.000 title claims abstract description 35
- 239000007791 liquid phase Substances 0.000 title claims abstract description 11
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 title claims description 4
- 230000003197 catalytic effect Effects 0.000 title abstract description 7
- -1 molybdenum halide Chemical class 0.000 claims abstract description 87
- 239000000203 mixture Substances 0.000 claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 29
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 8
- VVWFZKBKXPXGBH-UHFFFAOYSA-N 1,1,1,3,3-pentachloropropane Chemical compound ClC(Cl)CC(Cl)(Cl)Cl VVWFZKBKXPXGBH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 9
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 9
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- 239000010936 titanium Substances 0.000 abstract description 18
- 229910052719 titanium Inorganic materials 0.000 abstract description 18
- 239000011733 molybdenum Substances 0.000 abstract description 12
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 12
- 229910052758 niobium Inorganic materials 0.000 abstract description 7
- 239000010955 niobium Substances 0.000 abstract description 7
- 239000004604 Blowing Agent Substances 0.000 abstract description 4
- 239000003507 refrigerant Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 229910052718 tin Inorganic materials 0.000 description 14
- 239000007789 gas Substances 0.000 description 12
- 238000013022 venting Methods 0.000 description 12
- 238000004587 chromatography analysis Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 229910008046 SnC14 Inorganic materials 0.000 description 9
- 229910010066 TiC14 Inorganic materials 0.000 description 6
- 150000004820 halides Chemical class 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- ZDINGUUTWDGGFF-UHFFFAOYSA-N antimony(5+) Chemical compound [Sb+5] ZDINGUUTWDGGFF-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910000792 Monel Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000011437 continuous method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 2
- AOLPZAHRYHXPLR-UHFFFAOYSA-I pentafluoroniobium Chemical compound F[Nb](F)(F)(F)F AOLPZAHRYHXPLR-UHFFFAOYSA-I 0.000 description 2
- 239000003380 propellant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- YRGLXIVYESZPLQ-UHFFFAOYSA-I tantalum pentafluoride Chemical compound F[Ta](F)(F)(F)F YRGLXIVYESZPLQ-UHFFFAOYSA-I 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- UTACNSITJSJFHA-UHFFFAOYSA-N 1,1,1,3-tetrachloropropane Chemical compound ClCCC(Cl)(Cl)Cl UTACNSITJSJFHA-UHFFFAOYSA-N 0.000 description 1
- HJRXHKBZNQULJQ-UHFFFAOYSA-N 1,1,1-trichloro-2,2,3,3,3-pentafluoropropane Chemical class FC(F)(F)C(F)(F)C(Cl)(Cl)Cl HJRXHKBZNQULJQ-UHFFFAOYSA-N 0.000 description 1
- AVGQTJUPLKNPQP-UHFFFAOYSA-N 1,1,1-trichloropropane Chemical class CCC(Cl)(Cl)Cl AVGQTJUPLKNPQP-UHFFFAOYSA-N 0.000 description 1
- NDMMKOCNFSTXRU-UHFFFAOYSA-N 1,1,2,3,3-pentafluoroprop-1-ene Chemical class FC(F)C(F)=C(F)F NDMMKOCNFSTXRU-UHFFFAOYSA-N 0.000 description 1
- QAERDLQYXMEHEB-UHFFFAOYSA-N 1,1,3,3,3-pentafluoroprop-1-ene Chemical compound FC(F)=CC(F)(F)F QAERDLQYXMEHEB-UHFFFAOYSA-N 0.000 description 1
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 1
- NDKGUMMLYBINOC-UHFFFAOYSA-N 1,2-dichloro-1-fluoroethane Chemical compound FC(Cl)CCl NDKGUMMLYBINOC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910015221 MoCl5 Inorganic materials 0.000 description 1
- 241001653186 Mocis Species 0.000 description 1
- 101100425947 Mus musculus Tnfrsf13b gene Proteins 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical class ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000779 depleting effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/087—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated halogenated hydrocarbons
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/906—Comminution of transition metal containing catalyst
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/913—Vapor phase polymerization in absence of transition metal containing catalyst
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
A process for the catalytic fluorination of hydrochlorocarbons and hydrochlorofluorocarbons in the liquid phase. The process is useful for fluorinating hydrochloropropanes, hydrochlorofluoropropanes, hydrochloropropenes and hydrochlorofluoropropenes and most particularly useful for fluorinating 1, 1, 1,3,3-pentachloropropane to 1,1,1,3,3-pentafluoropropane. Suitable catalysts include (i) a pentavalent molybdenum halide; (ii) i; tetravalent tin halide; (iii) a tetravalent titanium halide; (iv) a mixture of a pentavalent tantalum halide with a tetravalent tin halide; (v) a mixture of a pentavalent tantalum halide with a tetravalent titanium halide; (vi) a mixture of a pentavalent niobium halide with a tetravalent tin halide; (vii) a mixture of a pentavalent niobium halide with a tetravalent titanium halide; (viii) a mixture of a pentavalent antimony halide with a tetravalent tin halide; (ix) a mixture of a pentavalent antimony halide with a tetravalent titanium halide; (x) a mixture of a pentavalent molybdenum halide with a tetravalent tin halide; (xi) a mixture of a pentavalent molybdenum halide with a tetravalent titanium halide and (xii) a mixture of a pentavalent antimony halide with a trivalent antimony halide. Products of this process are useful in a variety of applications including solvents, blowing agents, and refrigerants.
Description
LIOUID PHASE CATALYTIC FLUORINATION OF
HYDROCHLOROCARBON AND HYDROCHLOROFLUOROCARBON
BACKGROUND OF THE INVENTION
Field of the Invention The present invention relates to the fluorination of hydrochlorocarbons and hydrochlorofluorocarbons. More particularly, the invention pertains to the catalytic fluorination of hydrochlorocarbons and hydrochlorofluorocarbons in the liquid phase. The process is useful for fluorinating hydrochloropropanes, hydrochlorofluoropropanes, hydrochloropropenes and hydrochlorofluoropropenes and most particularly useful for fluorinating, 1, 1, 1,3,3-pentachloropropane to 1, 1, 1, 3,3 -pentafluoropropane.
Description of the Prior Art In recent years there has been universal concern that completely halogenated chlorofluorocarbons (CFCs) might be detrimental to the Earth's ozone layer.
Consequently, there is a worldwide effort to use fluorine-substituted hydrocarbons which contain fewer or no chlorine substituents.
i Hydrofluorocarbons (IIFCs) are of great interest due to their potential to replace ozone depleting CFCs and hydrochlorofluorocarbons (HCFCs) in a variety of applications such as solvents, blowing agents, refrigerants, cleaning agents, aerosol propellants, heat transfer media, dielectrics, fire extinguishing compositions and s power cycle working fluids. It is known in the art to produce fluorocarbons such as HFCs by reacting hydrogen fluoride with various hydrochlorocarbon compounds. In this regard, 1,1,1,3,3-pentafluoropropane (BFC-245fa), a hydrofluorocarbon having zero ozone depletion potential, is being considered as a replacement for CFCs such as dichlorodifluoromethane in refrigeration systems io and trichlorofluoromethane as a blowing agent. See U.S. Patent No.
HYDROCHLOROCARBON AND HYDROCHLOROFLUOROCARBON
BACKGROUND OF THE INVENTION
Field of the Invention The present invention relates to the fluorination of hydrochlorocarbons and hydrochlorofluorocarbons. More particularly, the invention pertains to the catalytic fluorination of hydrochlorocarbons and hydrochlorofluorocarbons in the liquid phase. The process is useful for fluorinating hydrochloropropanes, hydrochlorofluoropropanes, hydrochloropropenes and hydrochlorofluoropropenes and most particularly useful for fluorinating, 1, 1, 1,3,3-pentachloropropane to 1, 1, 1, 3,3 -pentafluoropropane.
Description of the Prior Art In recent years there has been universal concern that completely halogenated chlorofluorocarbons (CFCs) might be detrimental to the Earth's ozone layer.
Consequently, there is a worldwide effort to use fluorine-substituted hydrocarbons which contain fewer or no chlorine substituents.
i Hydrofluorocarbons (IIFCs) are of great interest due to their potential to replace ozone depleting CFCs and hydrochlorofluorocarbons (HCFCs) in a variety of applications such as solvents, blowing agents, refrigerants, cleaning agents, aerosol propellants, heat transfer media, dielectrics, fire extinguishing compositions and s power cycle working fluids. It is known in the art to produce fluorocarbons such as HFCs by reacting hydrogen fluoride with various hydrochlorocarbon compounds. In this regard, 1,1,1,3,3-pentafluoropropane (BFC-245fa), a hydrofluorocarbon having zero ozone depletion potential, is being considered as a replacement for CFCs such as dichlorodifluoromethane in refrigeration systems io and trichlorofluoromethane as a blowing agent. See U.S. Patent No.
2,942,036, Canadian 684,687, EP 381 986A, JP 02,272,086, WO 95/04022, U.S. Patent No.
5,496,866 (foam blowing agent) and European Patent No. 2,942,036 (aerosol propellant).
is Methods to produce HFC-245fa are also known in the art. See, e.g. WO
(reaction of 3-chloro-1,1, i,3,3-pentafluoropropane with hydrogen over a reduction catalyst); WO 94/29,251 (hydrogenation of 1,1,3,3,3-pentafluoropropene with hydrogen in the gas phase at 40-300 C using a palladium catalyst; European Patent 611,744 (hydrogenation of di- or trichloropropanes); U.S. Patent 2 o Number 5,574,192 (reaction of carbon tetrachloride with vinyl chloride to give CC13CH2CHC12 ( HCC-240fa) followed by fluorination with HF in the presence of a fluorination catalyst including pentavalent antimony, niobium, arsenic and tantalum halides and mixed halides). However, these methods are not without their shortcomings. For example, hydrogenation of mono-, di- or tri-chloropentafluoropropanes and unsaturated pentafluoropropene has several disadvantages, namely, multiple steps necessary for the preparation of s the feed materials, a higher reaction temperature and poor selectivity to the desired product. Fluorination of HCC-240fa with HF in the.presence of a pentavalent antimony halide catalyst shows a high corrosion rate when a metallic reactor is used. See U.S. Patent 4,138,355.
Also known in the art are reactions of unsaturated, halogenated olefins such as tri- and tetrachloroethenes with HF in the presence of tantalum pentafluoride, niobium pentafluoride, molybdenum pentachloride, and titanium tetrachloride.
See Feiring, A.E. in Journal of Fluorine Chemistry, 14, 7(1979); U.S. Patent 4,258,225 (tantalum pentafluoride and niobium pentafluoride as liquid; phase is catalysts).
Other known fluorination catalysts include tin salts or organotin compounds along with oxygen-containing compounds, see European Patent Application 187,643 (production of 1,1-dichloro-l-fluoroethane, HCFC-141 b), tin tetrachloride, see U.S.S.R. Patent 341,788 (liquid-phase process to produce 1,1-difluoroethane, HFC-152a from vinyl chloride), and mixtures of pentavalent and trivalent antimony halides, U.S. patent 4,138,355 (production of CF3CHZCHaCI, HCFC-153fb, from 1,1,1,3-tetrachloropropane, CC13CHZCH2Cl, HCC-250fb).
It would be advantageous to achieve the catalytic fluorination of HCCs and HCFCs with HF under less corrosive conditions using metal reactors. The use of tetravalent tin or titanium halide or an equal molar mixture of trivalent and pentavalent antimony halides or molybdenum pentahalide as a fluorination catalyst to fluorinate polychlorinated compounds with a-CHF,,Cl2-y, wherein y = 0 or 1 end group to give polyfluorinated compounds with a-CHF2 terminal group is not io known in the art. In particular, fluorination of HCC-240fa with HF to form HFC-245fa in the presence of tin, titanium, molybdenum or mixture of antimony(V) and antimony(III) halides is not known in the art.
i5 Si:m2MARY OF THE INVENTION
The invention provides a fluorinating process which comprises reacting at least one hydrochlorocarbon or hydrochlorofluorocarbon compound with hydrogen fluoride in the liquid phase and in the presence of at least one catalyst selected from the group consisting of (i) a pentavalent molybdenum halide of the formula MoC1s-ZFZ
20 wherein z is 0 to 5; (ii) a tetravalent tin halide of the formula SnC14.yFy wherein y is 0 to 4; (iii) a tetravalent titanium halide of the formula TiC14-xF,, wherein x is 0 to 4;
(iv) mixtures of a pentavalent tantalum halide of the fornlula TaC1sja wherein n is 0 to 5 with a tetravalent tin halide of the fonnula SnC14.,,Fy wherein y is 0 to 4; (v) mixtures of a pentavalent tantalum halide of the fonmila TaCl5-õF,, wherein n is 0 to with a tetravalent titanium halide of the fo;rmula TiC14.XF,, wherein x is 0 to 4; (vi) mixtures of a pentavalent niobium halide of the fonnula NbC15.,,,Fm wherein m is 0 5 to 5 with a tetravalent tin halide of the formula SnC14.YF,, wherein y is 0 to 4; (vii) mixtures of a pentavalent niobium halide of the formula NbC1s.,,,F. wherein m is 0 to 5 with a tetravalent titanium halide of the formula TiC14.xF,, wherein x is 0 to 4;
(viii) mixtures of a pentavalent antimony halide of the formula SbC1s pFP
wherein p is 0 to 5 with a tetravalent tin halide of the fbrmula SnClayFy wherein y is 0 to 4;
(ix) mixtures of a pentavalent antimony halide of the formula SbC15.PFP
wherein p is 0 to 5 with a tetravalent titanium halide of the fonnula TiCI~xFx wherein x is 0 to 4; (x) mixtures of a pentavalent molybdenum halide of the fonnula MoC1s.ZFZ
wherein z is 0 to 5 with a tetravalent tin halide of the formula SnC1a.yF,, wherein y is 0 to 4; (xi) mixtures of a pentavalent molybdenum halide of the formula is MoC15.ZF2 wherein z is 0 to 5 with a tetravalent titanium halide of the formula TiC14..,F,, wherein x is 0 to 4 and (xii) mixtures of a pentavalent antimony halide of the formula SbCIs.pFP wherein p is 0 to 5 with a trivalent antimony halide of the formula SbC13.PFP wherein p is 0 to 3.
The process of this invention achieves fluorination of HFCs and HCFCs under less corrosive conditions than prior art processes.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The invention concerns the catalytic fluorination of HCCs and HCFCs in the liquid phase with hydrogen fluoride. In the practice of the present invention, a liquid phase catalyst as described below is charged into a fluorination reactor prior to heating the s reactor. The reactor according to this invention may preferably be any suitable fluorination reaction pressure vessel or autoclave but preferably may be constructed from materials which are resistant to the corrosive effects of HF such as Hastelloy-C, Inconel, Monel and fluoropolymer-lined vessels. Such liquid phase fluorination reactors are well known in the art. Then the HF and the HCC or HCFC compound to be fluorinated and HF are fed to the reactor after the reactor reaches the desired temperature.
In the preferred embodiment, the reaction is conducted at a temperature of from about 50 C to about 2000 C, more preferably from about 90 C to about 140 C.
is In the preferred embodiment, the reaction is conducted for from about 1 to about 25 hours, more preferably from about 2 to about 8 hours. The pressure of the reaction is not critical and it varies depending on the quantity of hydrogen fluoride used, hydrogen chloride generated and conversion of organics. Convenient operating pressure ranges from about 50 to about 600 psig, and preferably from 50-400 psig. Pressure may be adjusted by continuously removing hydrogen chloride and volatile products from the reactor by distillation.
5,496,866 (foam blowing agent) and European Patent No. 2,942,036 (aerosol propellant).
is Methods to produce HFC-245fa are also known in the art. See, e.g. WO
(reaction of 3-chloro-1,1, i,3,3-pentafluoropropane with hydrogen over a reduction catalyst); WO 94/29,251 (hydrogenation of 1,1,3,3,3-pentafluoropropene with hydrogen in the gas phase at 40-300 C using a palladium catalyst; European Patent 611,744 (hydrogenation of di- or trichloropropanes); U.S. Patent 2 o Number 5,574,192 (reaction of carbon tetrachloride with vinyl chloride to give CC13CH2CHC12 ( HCC-240fa) followed by fluorination with HF in the presence of a fluorination catalyst including pentavalent antimony, niobium, arsenic and tantalum halides and mixed halides). However, these methods are not without their shortcomings. For example, hydrogenation of mono-, di- or tri-chloropentafluoropropanes and unsaturated pentafluoropropene has several disadvantages, namely, multiple steps necessary for the preparation of s the feed materials, a higher reaction temperature and poor selectivity to the desired product. Fluorination of HCC-240fa with HF in the.presence of a pentavalent antimony halide catalyst shows a high corrosion rate when a metallic reactor is used. See U.S. Patent 4,138,355.
Also known in the art are reactions of unsaturated, halogenated olefins such as tri- and tetrachloroethenes with HF in the presence of tantalum pentafluoride, niobium pentafluoride, molybdenum pentachloride, and titanium tetrachloride.
See Feiring, A.E. in Journal of Fluorine Chemistry, 14, 7(1979); U.S. Patent 4,258,225 (tantalum pentafluoride and niobium pentafluoride as liquid; phase is catalysts).
Other known fluorination catalysts include tin salts or organotin compounds along with oxygen-containing compounds, see European Patent Application 187,643 (production of 1,1-dichloro-l-fluoroethane, HCFC-141 b), tin tetrachloride, see U.S.S.R. Patent 341,788 (liquid-phase process to produce 1,1-difluoroethane, HFC-152a from vinyl chloride), and mixtures of pentavalent and trivalent antimony halides, U.S. patent 4,138,355 (production of CF3CHZCHaCI, HCFC-153fb, from 1,1,1,3-tetrachloropropane, CC13CHZCH2Cl, HCC-250fb).
It would be advantageous to achieve the catalytic fluorination of HCCs and HCFCs with HF under less corrosive conditions using metal reactors. The use of tetravalent tin or titanium halide or an equal molar mixture of trivalent and pentavalent antimony halides or molybdenum pentahalide as a fluorination catalyst to fluorinate polychlorinated compounds with a-CHF,,Cl2-y, wherein y = 0 or 1 end group to give polyfluorinated compounds with a-CHF2 terminal group is not io known in the art. In particular, fluorination of HCC-240fa with HF to form HFC-245fa in the presence of tin, titanium, molybdenum or mixture of antimony(V) and antimony(III) halides is not known in the art.
i5 Si:m2MARY OF THE INVENTION
The invention provides a fluorinating process which comprises reacting at least one hydrochlorocarbon or hydrochlorofluorocarbon compound with hydrogen fluoride in the liquid phase and in the presence of at least one catalyst selected from the group consisting of (i) a pentavalent molybdenum halide of the formula MoC1s-ZFZ
20 wherein z is 0 to 5; (ii) a tetravalent tin halide of the formula SnC14.yFy wherein y is 0 to 4; (iii) a tetravalent titanium halide of the formula TiC14-xF,, wherein x is 0 to 4;
(iv) mixtures of a pentavalent tantalum halide of the fornlula TaC1sja wherein n is 0 to 5 with a tetravalent tin halide of the fonnula SnC14.,,Fy wherein y is 0 to 4; (v) mixtures of a pentavalent tantalum halide of the fonmila TaCl5-õF,, wherein n is 0 to with a tetravalent titanium halide of the fo;rmula TiC14.XF,, wherein x is 0 to 4; (vi) mixtures of a pentavalent niobium halide of the fonnula NbC15.,,,Fm wherein m is 0 5 to 5 with a tetravalent tin halide of the formula SnC14.YF,, wherein y is 0 to 4; (vii) mixtures of a pentavalent niobium halide of the formula NbC1s.,,,F. wherein m is 0 to 5 with a tetravalent titanium halide of the formula TiC14.xF,, wherein x is 0 to 4;
(viii) mixtures of a pentavalent antimony halide of the formula SbC1s pFP
wherein p is 0 to 5 with a tetravalent tin halide of the fbrmula SnClayFy wherein y is 0 to 4;
(ix) mixtures of a pentavalent antimony halide of the formula SbC15.PFP
wherein p is 0 to 5 with a tetravalent titanium halide of the fonnula TiCI~xFx wherein x is 0 to 4; (x) mixtures of a pentavalent molybdenum halide of the fonnula MoC1s.ZFZ
wherein z is 0 to 5 with a tetravalent tin halide of the formula SnC1a.yF,, wherein y is 0 to 4; (xi) mixtures of a pentavalent molybdenum halide of the formula is MoC15.ZF2 wherein z is 0 to 5 with a tetravalent titanium halide of the formula TiC14..,F,, wherein x is 0 to 4 and (xii) mixtures of a pentavalent antimony halide of the formula SbCIs.pFP wherein p is 0 to 5 with a trivalent antimony halide of the formula SbC13.PFP wherein p is 0 to 3.
The process of this invention achieves fluorination of HFCs and HCFCs under less corrosive conditions than prior art processes.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The invention concerns the catalytic fluorination of HCCs and HCFCs in the liquid phase with hydrogen fluoride. In the practice of the present invention, a liquid phase catalyst as described below is charged into a fluorination reactor prior to heating the s reactor. The reactor according to this invention may preferably be any suitable fluorination reaction pressure vessel or autoclave but preferably may be constructed from materials which are resistant to the corrosive effects of HF such as Hastelloy-C, Inconel, Monel and fluoropolymer-lined vessels. Such liquid phase fluorination reactors are well known in the art. Then the HF and the HCC or HCFC compound to be fluorinated and HF are fed to the reactor after the reactor reaches the desired temperature.
In the preferred embodiment, the reaction is conducted at a temperature of from about 50 C to about 2000 C, more preferably from about 90 C to about 140 C.
is In the preferred embodiment, the reaction is conducted for from about 1 to about 25 hours, more preferably from about 2 to about 8 hours. The pressure of the reaction is not critical and it varies depending on the quantity of hydrogen fluoride used, hydrogen chloride generated and conversion of organics. Convenient operating pressure ranges from about 50 to about 600 psig, and preferably from 50-400 psig. Pressure may be adjusted by continuously removing hydrogen chloride and volatile products from the reactor by distillation.
In the preferred embodiment, the catalyst is present in an amount, based on the mole percent of HCC or HCFC or mixtures thereof of from about 2% to about 80%, and preferably from about 5% to about 50%, and most preferably from about 10% to about 20%. Fluorination catalysts having a purity of at least 98% are preferred.
Based on reaction stoichiometry, the required mole ratio of HF to organics (i.e.
HFCs and HCFCs) is at least equal to the riumber of chlorine atoms to be replaced in the starting organic material and preferably is relatively in an excess. In the preferred embodiment, the mole ratio of HF to HCC or HCFC compound ranges from at least about 1:1, more preferably from abou't 1:1 to about 15:1 and most preferably from about 6:1 to about 15:1.
Any water in the HF will react withi and deactivate the catalyst. Therefore i.s substantially anhydrous HF is preferred. By "substantially anhydrous" we mean that the HF contains less than about 0.05 vveight % water and preferably contains less than about 0.02 weight % water. However, one of ordinary skill in the art will appreciate that the presence of water in the catalyst can be compensated for by increasing the amount of catalyst used. HF suitable for use in the reaction may be purchased from AlliedSignal Inc. of Morristown, New Jersey.
Based on reaction stoichiometry, the required mole ratio of HF to organics (i.e.
HFCs and HCFCs) is at least equal to the riumber of chlorine atoms to be replaced in the starting organic material and preferably is relatively in an excess. In the preferred embodiment, the mole ratio of HF to HCC or HCFC compound ranges from at least about 1:1, more preferably from abou't 1:1 to about 15:1 and most preferably from about 6:1 to about 15:1.
Any water in the HF will react withi and deactivate the catalyst. Therefore i.s substantially anhydrous HF is preferred. By "substantially anhydrous" we mean that the HF contains less than about 0.05 vveight % water and preferably contains less than about 0.02 weight % water. However, one of ordinary skill in the art will appreciate that the presence of water in the catalyst can be compensated for by increasing the amount of catalyst used. HF suitable for use in the reaction may be purchased from AlliedSignal Inc. of Morristown, New Jersey.
In the preferred embodiment, the HCC or HCFC compound useful for the invention includes hydrochloroalkanes and hydrochlorofluoroalkanes having the formula CF,,Cl3_xCH2CHFyCl2_y, wherein x is 0 to 3 and y is 0 or 1. Of these hydrochloropropanes and hydrochlorofluoropropanes are more preferred. The most preferred hydrochloroalkanes and hydrochlorofluoroalkanes non-exclusively include CC13CH2CHC12, CFC12CH2CHC12, CF2C1CH2CHC12, CF3CH2CHC12, CF3CH2CHFCl, CC13CH2CHFCl, CFCI2CHZCHFCI, CFZCICHZCHFCI and mixtures thereof. The process of the present invention is most particularly useful for fluorinating 1, 1, 1, 3,3 -pentachloropropane to 1,1,1,3,3-pentafluoropropane.
Suitable HCCs and HCFCs also include hydrochloroalkenes and hydrochlorofluoroalkenes having the formula CF,,Cl3.xCH=CHY wherein x is 0 to 3 and Y is F or Cl. Of these, hydrochloropropenes and hydrochlorofluoropropenes are more preferred. The most preferred hydrochloroalkenes and hydrochlorofluoroalkenes non-exclusively include CC13CH=CHF, CC13CH=CHC1, CFCI2CH=CHF, CFC12CH=CHCI, CFZCICH=CHF, CFZCICH=CHCI, CF3CH=CHF, CF3CH=CHCI, and mixtures thereof.
Many of the HCCs and HCFCs materials to be fluorinated in the present invention are not commercially available. However, they may be prepared by any one of the known methods reported in the art. See B. Boutevin, et al., Monofunctional Vinyl ~ ~ ~
Chloride Telomers. 1. Synthesis and Characterization of Vinyl Chloride Telomer Standards, 18 Eur. Polym. J. 675 (1982) in 97 Chemical Abstracts 182966c (1982); and Kotora, et al., Selective Additions of Polyhalogenated Compounds to Chioro Substituted Ethenes Catalyzed by a Copper Complex, 44(2) React.Kinet.
s Catal. Lett. 415 (1991). See also the method disclosed in Examples I and 2 of U.S. patent number 5,574,192.
Suitable catalysts for use in the present invention include: (i) a pentavalent i o molybdenum halide of the formula MoC15.ZFZ wherein z is 0 to 5; (ii) a tetravalent tin halide of the formula SnC14yFy wherein y is 0 to 4; (iii) a tetravalent titanium halide of the formula TiCI~AFx wherein x is 0 to 4; (iv) mixtures of a pentavalent tantalum halide of the formula TaClsõFõ wherein n is 0 to 5 with a tetravalent tin halide of the formula SnC14yFY wherein y is 0 to 4; (v) mixtures of a pentavalent 15 tantalum halide of the formula TaC1s.QFn wherein n is 0 to 5 with a tetravalent titanium halide of the formula TiCI4.xF,, wherein x is 0 to 4; (vi) mixtures of a pentavalent niobium halide of the formula NbCls-.F. wherein m is 0 to 5 with a tetravalent tin halide of the formula SnC4.yFY wherein y is 0 to 4; (vii) mixtures of a pentavalent niobium halide of the formula NbCls-0,Fm wherein m is 0 to 5 with a 20 tetravalent titanium halide of the formula TiC14.xFx wherein x is 0 to 4;
(viii) mixtures of a pentavalent antimony halide of the formula SbC13.PFP wherein p is 0 to 5 with a tetravalent tin halide of the formula SnC14.yFy wherein y is 0 to 4; (ix) mixtures of a pentavalent antimony halide of the formula SbC1S-PFp wherein p is 0 to 5 with a tetravalent titanium halide of the formula TiC14xF, wherein x is 0 to 4;
(x) mixtures of a pentavalent molybdenum halide of the formula MoC1S_ZFZ
wherein z is 0 to 5 with a tetravalent tin halide of the formula SnCI4.,Fy wherein y is 0 to 4;
(xi) mixtures of a pentavalent molybdenum halide of the formula MoC15_ZFZ
wherein z is 0 to 5 with a tetravalent titanium halide of the formula TiC14xFX
wherein x is 0 to 4 and (xii) mixtures of a pentavalent antimony haGde of the formula SbCI5.QFp wherein p is 0 to 5 with a trivalent antimony halide of the formula SbC13-pFp wherein p is 0 to 3.
In the preferred embodiment, for group (iv) through (xii) catalysts above, the molar ratios of the components of the mixtures typically range from about 1:9 to about 9:1, preferably from about 3:7 to about 7:3 and most preferably about 1:1. Of the above, the preferred catalysts are pentavalent molybdenum halides, a tetravalent tin halides, a tetravalent titanium halides, and mixtures of a pentavalent antimony halides or mixed halides with a trivalent antimony halides or mixed halides. The term "niixed halide" means more than one different halide is present in the compound. The most preferred catalysts are tin tetrahalide and mixtures of TaC1s and SnC14.
If in the course of conducting the inventive process the catalyst decreases in catalytic effectiveness, it can be regenerated. One method of regenerating the f 1 ' I
catalyst is to treat it by flowing a stream of <<n excess of gaseous chlorine over the catalyst for from about I to about 2 hours ai: a temperature of from about 65 C to about 100 C.
Resulting fluorination products such as HFC-245fa may be recovered from the reaction mixture via any separation and purification method known in the art such as neutralization and distillation. The process may be carried out either in a batch or continuous method. In a continuous process, the HCC or HCFC compound to be fluorinated and HF are preferably fed simultaneously to the reactor after the reactor reaches the desired temperature. The temperature and pressure of the fluorination reaction remain the same for both the batch and continuous modes of operation. The residence time for a continuous process varies from about I
second to about 2 hours, preferably from about 5 seconds to about 1 hour and most preferably from about 10 seconds to about 30 minutes. The catalyst concentration is not critical for a continuous process. A sufficient quantity of catalyst must be present to effect the fluorination in the residence times described above. The continuous method requires the removal of fluorination products and hydrogen chloride from the reactor continuously as it is formed. Unreacted HF
and under-fluorinated materials such as CFC12CH2CHC12; CF2C1CH2CHC12;
CF3CH2CHClZ; CF3CH2CHFCI, CC13CH2CHFC1; CFCI2CH2CHFCI;
CFZCICHZCHFCI; CF3CH=CHF, CF3CH=C'HCI; CC13CH=CHF; CFCI2CH=CHF;
ii CFC12CH=CHCI; CF2CICH=CHF and CF2CICH=CHCI may be recycled back to the same reactor or optionally to a separate reactor.
The following non-limiting examples serve to illustrate the invention.
EXAMPLE 1: Fluorination of CCIzCHZCHCI, with HF/SnCL
A 600 ml Monel autoclave equipped with a magnetic drive was charged with 9.4 g SnC14 and cooled to -20 C. The autoclave was then evacuated and charged with 60.5 g anhydrous HF. The contents were cooled to -25 C and 54 g CC13CH2CHC12 was added thereto. The autoclave was then connected to a packed column/condenser assembly, and the condenser was maintained at -5 C. The colunuVcondenser assembly serves to vent off gaseous HCI and effect a HCI/HF
separation. The reaction mixture was heated with stirring to about 135 C over hours and maintained at that temperature for an additional 3 hours. During this period, the pressure in the autoclave was maintained between 300-400 psig by periodically venting pressure in excess of 400 psig. Venting was done from the top of the condenser to an aqueous KOH scrubber which was connected to two -78 C cold traps. The reactor was then completely vented to the cold traps to give 33.2 g of product. Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages:
CF3CH2CHF2 (57), CF3CH2CHFC1(9), CF3CH=CHF (3), CF3CH=CHC1(30) and C6 materials (1). Relative area percentages in these examples closely approximates weight percent.
EXAMPLE 2: Fluorination of CCI;CH,CHCh with HF/TiC14 s The experiment described in Example I was repeated except that TiC14 was used as the catalyst. To the apparatus described in Example 1 was charged 6.8 g TiCl4, 63.1 g HF and 54 g CC13CHZCHCI2. This nzixture was heated with stirring to about 135 C in 2 hours and maintained at that temperature for an additional 3 hours. Venting the reactor completely to the cold traps gave 17.3 g of product.
Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages: CF3CH2CHF2 (25), CF3CH2CHFCI
(16), CF3CH=CHF (3), CF3CH=CHC1(55) and C6 materials (1).
EXAMPLE 3: Fluorination of CCl3CH2CH.Cl-2 with HF/MoCh 1s The experiment described in Example I was repeated except that MoCl5 was used as the catalyst. To the apparatus described in Example 1 was charged 10.0 g MoCIs, 65.3g HF and 54.19 CC13CH2CHC12. This mixture was heated with stirring to about 135 C in 2 hours and maintained at that temperature for an additional 3 hours. Venting the reactor completely to the cold traps gave 15.0 g of product.
Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages: CF3CH2CHF2 (44), CF3CH2CHFCI
(15), CF3CH=CHF (3), CF3CH=CHC1(37) and C6 materials (1).
EXAMPLE 4: Fluorination of CCl;CH2CHCI:, with HF/SbCI5/S bCi3 The experiment described in Example 1 was repeated except that an equal molar mixture of SbC15 and SbC13 was used as the catalyst. To the apparatus described in Example 1 was charged 5.4 g SbC15, 4.1 g SbCl3, 60.2 g HF and 54 g CC13CH2CHClZ. This mixture was heated with stirring to about 135 C in 2 hours and maintained at that temperature for an additional 3 hours. Venting the reactor completely to the cold traps gave 26.8 g of product. Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages: CF3CH2CHF2 (91), CF3CH2CHFCI (5), CF3CH=CHF (1), CF3CH=CHC1(2) and C6 materials (1).
EXAMPLE 5: Fluorination of CCI3CHZCHCI2 with HF/TaCIs/SnCh 1s The experiment described in Example I was repeated except that an equimolar mixture of TaC15 and SnC14 was used as the catalyst. To the apparatus described in Example 1 was charged 6.5 g of TaC13, 4.7 g SnC4, 64.0 g HF and 54 g CC13CH2CHC12. This mixture was heated with stirring to about 126 C in 2 hours and maintained at that temperature for an additional 3 hours. Venting the reactor completely to the cold traps gave 32.6 g of product. Gas chromatographic analysis of the product showed the presence of the following products with their relative i ~ T i area percentages: CF3CH2CHF2 (91), CF3CH2CHFCl (1.3), CF3CH=CHF (0.2), CF3CH=CHCI (7.1) and C6 materials (0.4).
EXAMPLE 6: Fluorination of CC13CH2,CHC1, with HF/SnCl4 at 125 C
The experiment described in Example 1 was repeated except that the fluorination was conducted at 125 C. To the apparatus described in Example 1 was charged 9.4 g SnC14, 65.9 g HF and 54 g CC13CH2CHC12. This mixture was heated with stirring to about 125 C in 2 hours and maintained at that temperature for an additional 3 hours. Venting the reactor completely to the cold traps gave 23.8 g of product. Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages: CF3CH2CHF2 (40), CF3CH2CHFC1(19), CF3CH=CHF (3), CF:.1CH=CHCI (37) and C6 materials (1).
EXAMPLE 7: Fluorination of CF3CH= HF with HF/SnClg at 115 C
i5 The experiment described in Example 1 was repeated except that CF3CH=CHF
was used as the starting material. To the apparatus described in Example 1 was charged 18.8 g SnC14, 42.4 g HF and 57.4 g CF3CH=CHF. This mixture was heated with stirring to about 1 15 C in 2 hours and maintained at that temperature for an additional 3 hours. Venting the reactor conipletely to the cold traps gave 52.6 g of product. Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages: CF3CH2CHF2 (39), CF3CH2CHFC1(2), CF3CH=CHF (47), anci CF3CH=CHCI (11).
i5 EXAMPLE 8: Fluorination of CF3CH=CHF with HF/SbCl at 930 C
The experiment described in Example 1 was repeated except that SbC1S and CF3CH=CHF were used as the catalyst and the starting material. To the apparatus described in Example 1 was charged 21.6 g SbC15, 36.0 g HF and 59.2 g CF3CH=CHF. This mixture was heated with stirring to about 93 C in 2 hours and maintained at that temperature for an additional 3 hours. Venting the reactor completely to the cold traps gave 48.0 g of product. Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages: CF3CH2CHF2 (90), CF3CH2CHFC1(4), CF3CH=CHF (1), CF3CH=CHCI (3) and high boilers (2).
EXAMPLE 9: Fluorination of CF3CH=CHF with HF/TaCls at 1170 C
The experiment described in Example I was repeated except that TaC15 and CF3CH=CHF were used as the catalyst and the starting material. To the apparatus described in Example I was charged 25.8 g TaCls, 36.8 g HF and 57.3 g CF3CH=CHF. This mixture was heated with stirring to about 117 C in 2 hours and maintained at that temperature for an additional 3 hours. Venting the reactor completely to the cold traps gave 48.3 g of product. Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages: CF3CH2CHF2 (98), CF3CH=CHF (1), and CF3CH=CHC1(1).
r ~ i EXAMPLE 10: Fluorination of CF3CH=CHCI with HF/SbCli at 950 C
The experiment described in Example I was repeated except that SbC15 and CF3CH=CHCI were used as the catalyst and the starting material. To the apparatus s described in Example I was charged 22.4 g SbC13, 45.3 g HF and 75.2 g CF3CH=CHCI. This mixture was heated with stirring to about 95 C in 1 hour and maintained at that temperature for an additional 4 hours. Venting the reactor completely to the cold traps gave 72.9 g of product. Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages: CF3CH2CHF2(83), CF3CH2CHFCI (5), CF3CH=CHF (1), CF3CH=CHCI (9), CF2CICH2CHClZ (1) and CC13CH2CHCI2 (1).
EXAIVIl'LE 11: Fluorination of CF3CH=C:HCI with HF/TaCls at 116 C
The experiment described in Example I was repeated except that TaC15 and is CF3CH=CHCI were used as the catalyst and the starting material. To the apparatus described in Example 1 was charged 26.9 g; TaC15, 47.5 g HF and 76.4 g CF3CH=CHCI. This mixture was heated with stirring to about 116 C in 1 hour and maintained at that temperature for an additiional 4 hours. Venting the reactor completely to the cold traps gave 79.5 g of' product. Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages: CF3CH2CHF2 (97), CF3C'H2CHFC1(1), CF3CH=CHF (traces), ).
CF3CH=CHC1(1), and CF2C1CH2CHC12 (1).
i~
Suitable HCCs and HCFCs also include hydrochloroalkenes and hydrochlorofluoroalkenes having the formula CF,,Cl3.xCH=CHY wherein x is 0 to 3 and Y is F or Cl. Of these, hydrochloropropenes and hydrochlorofluoropropenes are more preferred. The most preferred hydrochloroalkenes and hydrochlorofluoroalkenes non-exclusively include CC13CH=CHF, CC13CH=CHC1, CFCI2CH=CHF, CFC12CH=CHCI, CFZCICH=CHF, CFZCICH=CHCI, CF3CH=CHF, CF3CH=CHCI, and mixtures thereof.
Many of the HCCs and HCFCs materials to be fluorinated in the present invention are not commercially available. However, they may be prepared by any one of the known methods reported in the art. See B. Boutevin, et al., Monofunctional Vinyl ~ ~ ~
Chloride Telomers. 1. Synthesis and Characterization of Vinyl Chloride Telomer Standards, 18 Eur. Polym. J. 675 (1982) in 97 Chemical Abstracts 182966c (1982); and Kotora, et al., Selective Additions of Polyhalogenated Compounds to Chioro Substituted Ethenes Catalyzed by a Copper Complex, 44(2) React.Kinet.
s Catal. Lett. 415 (1991). See also the method disclosed in Examples I and 2 of U.S. patent number 5,574,192.
Suitable catalysts for use in the present invention include: (i) a pentavalent i o molybdenum halide of the formula MoC15.ZFZ wherein z is 0 to 5; (ii) a tetravalent tin halide of the formula SnC14yFy wherein y is 0 to 4; (iii) a tetravalent titanium halide of the formula TiCI~AFx wherein x is 0 to 4; (iv) mixtures of a pentavalent tantalum halide of the formula TaClsõFõ wherein n is 0 to 5 with a tetravalent tin halide of the formula SnC14yFY wherein y is 0 to 4; (v) mixtures of a pentavalent 15 tantalum halide of the formula TaC1s.QFn wherein n is 0 to 5 with a tetravalent titanium halide of the formula TiCI4.xF,, wherein x is 0 to 4; (vi) mixtures of a pentavalent niobium halide of the formula NbCls-.F. wherein m is 0 to 5 with a tetravalent tin halide of the formula SnC4.yFY wherein y is 0 to 4; (vii) mixtures of a pentavalent niobium halide of the formula NbCls-0,Fm wherein m is 0 to 5 with a 20 tetravalent titanium halide of the formula TiC14.xFx wherein x is 0 to 4;
(viii) mixtures of a pentavalent antimony halide of the formula SbC13.PFP wherein p is 0 to 5 with a tetravalent tin halide of the formula SnC14.yFy wherein y is 0 to 4; (ix) mixtures of a pentavalent antimony halide of the formula SbC1S-PFp wherein p is 0 to 5 with a tetravalent titanium halide of the formula TiC14xF, wherein x is 0 to 4;
(x) mixtures of a pentavalent molybdenum halide of the formula MoC1S_ZFZ
wherein z is 0 to 5 with a tetravalent tin halide of the formula SnCI4.,Fy wherein y is 0 to 4;
(xi) mixtures of a pentavalent molybdenum halide of the formula MoC15_ZFZ
wherein z is 0 to 5 with a tetravalent titanium halide of the formula TiC14xFX
wherein x is 0 to 4 and (xii) mixtures of a pentavalent antimony haGde of the formula SbCI5.QFp wherein p is 0 to 5 with a trivalent antimony halide of the formula SbC13-pFp wherein p is 0 to 3.
In the preferred embodiment, for group (iv) through (xii) catalysts above, the molar ratios of the components of the mixtures typically range from about 1:9 to about 9:1, preferably from about 3:7 to about 7:3 and most preferably about 1:1. Of the above, the preferred catalysts are pentavalent molybdenum halides, a tetravalent tin halides, a tetravalent titanium halides, and mixtures of a pentavalent antimony halides or mixed halides with a trivalent antimony halides or mixed halides. The term "niixed halide" means more than one different halide is present in the compound. The most preferred catalysts are tin tetrahalide and mixtures of TaC1s and SnC14.
If in the course of conducting the inventive process the catalyst decreases in catalytic effectiveness, it can be regenerated. One method of regenerating the f 1 ' I
catalyst is to treat it by flowing a stream of <<n excess of gaseous chlorine over the catalyst for from about I to about 2 hours ai: a temperature of from about 65 C to about 100 C.
Resulting fluorination products such as HFC-245fa may be recovered from the reaction mixture via any separation and purification method known in the art such as neutralization and distillation. The process may be carried out either in a batch or continuous method. In a continuous process, the HCC or HCFC compound to be fluorinated and HF are preferably fed simultaneously to the reactor after the reactor reaches the desired temperature. The temperature and pressure of the fluorination reaction remain the same for both the batch and continuous modes of operation. The residence time for a continuous process varies from about I
second to about 2 hours, preferably from about 5 seconds to about 1 hour and most preferably from about 10 seconds to about 30 minutes. The catalyst concentration is not critical for a continuous process. A sufficient quantity of catalyst must be present to effect the fluorination in the residence times described above. The continuous method requires the removal of fluorination products and hydrogen chloride from the reactor continuously as it is formed. Unreacted HF
and under-fluorinated materials such as CFC12CH2CHC12; CF2C1CH2CHC12;
CF3CH2CHClZ; CF3CH2CHFCI, CC13CH2CHFC1; CFCI2CH2CHFCI;
CFZCICHZCHFCI; CF3CH=CHF, CF3CH=C'HCI; CC13CH=CHF; CFCI2CH=CHF;
ii CFC12CH=CHCI; CF2CICH=CHF and CF2CICH=CHCI may be recycled back to the same reactor or optionally to a separate reactor.
The following non-limiting examples serve to illustrate the invention.
EXAMPLE 1: Fluorination of CCIzCHZCHCI, with HF/SnCL
A 600 ml Monel autoclave equipped with a magnetic drive was charged with 9.4 g SnC14 and cooled to -20 C. The autoclave was then evacuated and charged with 60.5 g anhydrous HF. The contents were cooled to -25 C and 54 g CC13CH2CHC12 was added thereto. The autoclave was then connected to a packed column/condenser assembly, and the condenser was maintained at -5 C. The colunuVcondenser assembly serves to vent off gaseous HCI and effect a HCI/HF
separation. The reaction mixture was heated with stirring to about 135 C over hours and maintained at that temperature for an additional 3 hours. During this period, the pressure in the autoclave was maintained between 300-400 psig by periodically venting pressure in excess of 400 psig. Venting was done from the top of the condenser to an aqueous KOH scrubber which was connected to two -78 C cold traps. The reactor was then completely vented to the cold traps to give 33.2 g of product. Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages:
CF3CH2CHF2 (57), CF3CH2CHFC1(9), CF3CH=CHF (3), CF3CH=CHC1(30) and C6 materials (1). Relative area percentages in these examples closely approximates weight percent.
EXAMPLE 2: Fluorination of CCI;CH,CHCh with HF/TiC14 s The experiment described in Example I was repeated except that TiC14 was used as the catalyst. To the apparatus described in Example 1 was charged 6.8 g TiCl4, 63.1 g HF and 54 g CC13CHZCHCI2. This nzixture was heated with stirring to about 135 C in 2 hours and maintained at that temperature for an additional 3 hours. Venting the reactor completely to the cold traps gave 17.3 g of product.
Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages: CF3CH2CHF2 (25), CF3CH2CHFCI
(16), CF3CH=CHF (3), CF3CH=CHC1(55) and C6 materials (1).
EXAMPLE 3: Fluorination of CCl3CH2CH.Cl-2 with HF/MoCh 1s The experiment described in Example I was repeated except that MoCl5 was used as the catalyst. To the apparatus described in Example 1 was charged 10.0 g MoCIs, 65.3g HF and 54.19 CC13CH2CHC12. This mixture was heated with stirring to about 135 C in 2 hours and maintained at that temperature for an additional 3 hours. Venting the reactor completely to the cold traps gave 15.0 g of product.
Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages: CF3CH2CHF2 (44), CF3CH2CHFCI
(15), CF3CH=CHF (3), CF3CH=CHC1(37) and C6 materials (1).
EXAMPLE 4: Fluorination of CCl;CH2CHCI:, with HF/SbCI5/S bCi3 The experiment described in Example 1 was repeated except that an equal molar mixture of SbC15 and SbC13 was used as the catalyst. To the apparatus described in Example 1 was charged 5.4 g SbC15, 4.1 g SbCl3, 60.2 g HF and 54 g CC13CH2CHClZ. This mixture was heated with stirring to about 135 C in 2 hours and maintained at that temperature for an additional 3 hours. Venting the reactor completely to the cold traps gave 26.8 g of product. Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages: CF3CH2CHF2 (91), CF3CH2CHFCI (5), CF3CH=CHF (1), CF3CH=CHC1(2) and C6 materials (1).
EXAMPLE 5: Fluorination of CCI3CHZCHCI2 with HF/TaCIs/SnCh 1s The experiment described in Example I was repeated except that an equimolar mixture of TaC15 and SnC14 was used as the catalyst. To the apparatus described in Example 1 was charged 6.5 g of TaC13, 4.7 g SnC4, 64.0 g HF and 54 g CC13CH2CHC12. This mixture was heated with stirring to about 126 C in 2 hours and maintained at that temperature for an additional 3 hours. Venting the reactor completely to the cold traps gave 32.6 g of product. Gas chromatographic analysis of the product showed the presence of the following products with their relative i ~ T i area percentages: CF3CH2CHF2 (91), CF3CH2CHFCl (1.3), CF3CH=CHF (0.2), CF3CH=CHCI (7.1) and C6 materials (0.4).
EXAMPLE 6: Fluorination of CC13CH2,CHC1, with HF/SnCl4 at 125 C
The experiment described in Example 1 was repeated except that the fluorination was conducted at 125 C. To the apparatus described in Example 1 was charged 9.4 g SnC14, 65.9 g HF and 54 g CC13CH2CHC12. This mixture was heated with stirring to about 125 C in 2 hours and maintained at that temperature for an additional 3 hours. Venting the reactor completely to the cold traps gave 23.8 g of product. Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages: CF3CH2CHF2 (40), CF3CH2CHFC1(19), CF3CH=CHF (3), CF:.1CH=CHCI (37) and C6 materials (1).
EXAMPLE 7: Fluorination of CF3CH= HF with HF/SnClg at 115 C
i5 The experiment described in Example 1 was repeated except that CF3CH=CHF
was used as the starting material. To the apparatus described in Example 1 was charged 18.8 g SnC14, 42.4 g HF and 57.4 g CF3CH=CHF. This mixture was heated with stirring to about 1 15 C in 2 hours and maintained at that temperature for an additional 3 hours. Venting the reactor conipletely to the cold traps gave 52.6 g of product. Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages: CF3CH2CHF2 (39), CF3CH2CHFC1(2), CF3CH=CHF (47), anci CF3CH=CHCI (11).
i5 EXAMPLE 8: Fluorination of CF3CH=CHF with HF/SbCl at 930 C
The experiment described in Example 1 was repeated except that SbC1S and CF3CH=CHF were used as the catalyst and the starting material. To the apparatus described in Example 1 was charged 21.6 g SbC15, 36.0 g HF and 59.2 g CF3CH=CHF. This mixture was heated with stirring to about 93 C in 2 hours and maintained at that temperature for an additional 3 hours. Venting the reactor completely to the cold traps gave 48.0 g of product. Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages: CF3CH2CHF2 (90), CF3CH2CHFC1(4), CF3CH=CHF (1), CF3CH=CHCI (3) and high boilers (2).
EXAMPLE 9: Fluorination of CF3CH=CHF with HF/TaCls at 1170 C
The experiment described in Example I was repeated except that TaC15 and CF3CH=CHF were used as the catalyst and the starting material. To the apparatus described in Example I was charged 25.8 g TaCls, 36.8 g HF and 57.3 g CF3CH=CHF. This mixture was heated with stirring to about 117 C in 2 hours and maintained at that temperature for an additional 3 hours. Venting the reactor completely to the cold traps gave 48.3 g of product. Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages: CF3CH2CHF2 (98), CF3CH=CHF (1), and CF3CH=CHC1(1).
r ~ i EXAMPLE 10: Fluorination of CF3CH=CHCI with HF/SbCli at 950 C
The experiment described in Example I was repeated except that SbC15 and CF3CH=CHCI were used as the catalyst and the starting material. To the apparatus s described in Example I was charged 22.4 g SbC13, 45.3 g HF and 75.2 g CF3CH=CHCI. This mixture was heated with stirring to about 95 C in 1 hour and maintained at that temperature for an additional 4 hours. Venting the reactor completely to the cold traps gave 72.9 g of product. Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages: CF3CH2CHF2(83), CF3CH2CHFCI (5), CF3CH=CHF (1), CF3CH=CHCI (9), CF2CICH2CHClZ (1) and CC13CH2CHCI2 (1).
EXAIVIl'LE 11: Fluorination of CF3CH=C:HCI with HF/TaCls at 116 C
The experiment described in Example I was repeated except that TaC15 and is CF3CH=CHCI were used as the catalyst and the starting material. To the apparatus described in Example 1 was charged 26.9 g; TaC15, 47.5 g HF and 76.4 g CF3CH=CHCI. This mixture was heated with stirring to about 116 C in 1 hour and maintained at that temperature for an additiional 4 hours. Venting the reactor completely to the cold traps gave 79.5 g of' product. Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages: CF3CH2CHF2 (97), CF3C'H2CHFC1(1), CF3CH=CHF (traces), ).
CF3CH=CHC1(1), and CF2C1CH2CHC12 (1).
i~
Claims (11)
1. A fluorinating process which comprises reacting at least one hydrochlorocarbon or hydrochlorofluorocarbon compound with hydrogen fluoride in the liquid phase and in the presence of a catalyst comprising, in combination, a pentavalent tantalum halide of the formula TaC15-nFn wherein n is 0 to 5 and a tetravalent tin halide of the formula SnCl4-yFy wherein y is 0 to 4.
2. The process of claim 1 wherein the hydrochlorocarbon or hydrochlorofluorocarbon compound is a hydrochloropropane or hydrochlorofluoropropane.
3. The process of claim 1 wherein the hydrochlorocarbon or hydrochlorofluorocarbon comprises a compound described by the formula CFxCl3-XCH2CHFyCl2-y1 wherein x is 0 to 3 and y is 0 or 1 and the product of the fluorination process comprises 1,1,1,3,3-pentafluoropropane.
4. The process of claim 3 wherein the molar ratio of hydrogen fluoride to the compound described by the formula CFXCI3,CH2CHFyCl2_,, is from 6:1 to about 15:1 and the catalyst is present in an amount of from about 10% to about 20% based on the mole percent of compound described by the formula CFXCI3_XCH2CHF,,CI2_y and the reaction is conducted at a temperature of from about 90 C to about 140 C
for a period of 2-8 hours to produce 1,1,1,3,3pentafluoropropane.
for a period of 2-8 hours to produce 1,1,1,3,3pentafluoropropane.
5. The process of claim 1 which comprises reacting CCl3CH2CHCl2 with hydrogen fluoride and an equimolar mixture of TaC15 and SnCl4 as catalyst in the liquid phase, wherein the molar ratio of hydrogen fluoride to CCl3CH2CHCl2 is from 6:1 to about 15:1 and the catalyst is present in an amount of from about 10%
to about 20% based on the mole percent of CCl3CH2CHCl2 and the reaction is conducted at a temperature of from about 90 C to about 140 C for a period of hours to produce 1,1,1,3,3-pentafluoropropane.
to about 20% based on the mole percent of CCl3CH2CHCl2 and the reaction is conducted at a temperature of from about 90 C to about 140 C for a period of hours to produce 1,1,1,3,3-pentafluoropropane.
6. A fluorinating process which comprises reacting at least one hydrochlorocarbon or hydrochlorofluorocarbon compound with hydrogen fluoride in the liquid phase and in the presence of at least one catalyst selected from the group consisting of (i) a mixture of a pentavalent antimony halide of the formula SbCl5-pFp wherein p is 0 to 5 with a tetravalent tin halide of the formula SnCl4-xFx wherein x is 0 to 4; and (ii) a mixture of a pentavalent antimony halide of the formula SbCl5-p F p wherein p is 0 to 5 with a trivalent antimony halide of the formula SbCl3-p F
p wherein p is 0 to 3 to form 1,1,1,3,3-pentafluoropropane.
p wherein p is 0 to 3 to form 1,1,1,3,3-pentafluoropropane.
7. The process of claim 6 wherein the hydrochlorocarbon or hydrochlorofluorocarbon compound is a hydrochloropropane or hydrochlorofluoropropane.
8. The process of claim 6 wherein the hydrochlorocarbon or hydrochlorofluorocarbon comprises a compound described by has the formula CF x Cl3-x CH2CHF y Cl2-y, wherein x is 0 to 3 and y is 0 or 1.
9. The process of claim 6 wherein the hydrochlorocarbon or hydrochlorofluorocarbon compound is selected from the group consisting of CCl3CH2CHCl2, CFCl2CH2CHCl2, CF2ClCH2CHl2, CF3CH2CHCl2, CF3CH2CHFCl, CCl3CH2CHFCl, CFCl2CH2CHFCl, CF2ClCH2CHFCl and mixtures thereof.
10. The process of claim 6 wherein the hydrochlorocarbon or hydrochlorofluorocarbon compound is selected from the group consisting of CCl3CH=CHF, CCl3CH=CHCl, CFCl2CH=CHF, CFFCl2CH=CHCl, CF2ClCH=CHF, CF2ClCH=CHCl, CF3CH=CHF and CF3CH=CHCl.
11. The process of claim 6 wherein the hydrochlorocarbon comprises 1,1,1,3,3pentachloropropane.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/744,157 | 1996-11-12 | ||
| US08/744,157 US6023004A (en) | 1996-11-12 | 1996-11-12 | Liquid phase catalytic fluorination of hydrochlorocarbon and hydrochlorofluorocarbon |
| PCT/US1997/020448 WO1998021171A1 (en) | 1996-11-12 | 1997-11-12 | Liquid phase catalytic fluorination of hydrochlorocarbon and hydrochlorofluorocarbon |
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|---|---|
| CA2271341A1 CA2271341A1 (en) | 1998-05-22 |
| CA2271341C true CA2271341C (en) | 2007-06-12 |
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| CA002271341A Expired - Lifetime CA2271341C (en) | 1996-11-12 | 1997-11-12 | Liquid phase catalytic fluorination of hydrochlorocarbon and hydrochlorofluorocarbon |
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|---|---|
| US (2) | US6023004A (en) |
| EP (2) | EP1104748A3 (en) |
| JP (1) | JP3389251B2 (en) |
| KR (1) | KR100583800B1 (en) |
| AU (1) | AU5432498A (en) |
| CA (1) | CA2271341C (en) |
| DE (1) | DE69707490T2 (en) |
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| WO (1) | WO1998021171A1 (en) |
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| JP3407379B2 (en) * | 1993-06-10 | 2003-05-19 | ダイキン工業株式会社 | Method for producing 1,1,1,3,3-pentafluoropropane |
| US5395997A (en) * | 1993-07-29 | 1995-03-07 | Alliedsignal Inc. | Process for the preparation of hydrofluorocarbons having 3 to 7 carbon atoms |
| DE69414403T2 (en) * | 1993-07-29 | 1999-05-06 | Alliedsignal Inc., Morristown, N.J. | METHOD FOR PRODUCING 1,1,1,3,3 PENTAFLUORPROPANE |
| US5608126A (en) * | 1994-06-28 | 1997-03-04 | Ag Technology Co., Ltd. | Process for preparing 1,1,1,3,3-pentafluoropropane |
| CA2194151C (en) * | 1994-07-01 | 2006-12-12 | Yasufu Yamada | Process for producing difluoromethane |
| KR100240375B1 (en) * | 1994-07-11 | 2000-01-15 | 크리스 로저 에이치 | Method for preparing 1,1,1,3,3-pentafluoropropane |
| JP3213929B2 (en) * | 1994-07-14 | 2001-10-02 | ダイキン工業株式会社 | Method for producing 1,1,1,2,3,3,3-heptafluoropropane |
| FR2724928B1 (en) * | 1994-09-26 | 1996-10-31 | Atochem Elf Sa | SYNTHESIS OF 1,1,1,3,3-PENTAFLUOROPROPANE |
| FR2731703B1 (en) * | 1995-03-16 | 1997-05-30 | Solvay | PROCESS FOR THE PREPARATION OF DIFLUOROMETHANE |
| US5545775A (en) * | 1995-08-25 | 1996-08-13 | Alliedsignal Inc. | Liquid phase process for the preparation of 1,1-difluoroethane |
| FR2740132B1 (en) * | 1995-10-23 | 1997-12-19 | Solvay | PROCESS FOR THE PREPARATION OF 1,1,1,3,3-PENTAFLUOROPROPANE |
| US6268540B1 (en) * | 1996-06-24 | 2001-07-31 | Alliedsignal Inc. | Catalyst and process for the fluorination of hydrohalomethanes |
-
1996
- 1996-11-12 US US08/744,157 patent/US6023004A/en not_active Expired - Lifetime
-
1997
- 1997-11-12 KR KR1019997004154A patent/KR100583800B1/en not_active IP Right Cessation
- 1997-11-12 DE DE69707490T patent/DE69707490T2/en not_active Expired - Lifetime
- 1997-11-12 AU AU54324/98A patent/AU5432498A/en not_active Abandoned
- 1997-11-12 CA CA002271341A patent/CA2271341C/en not_active Expired - Lifetime
- 1997-11-12 EP EP01103592A patent/EP1104748A3/en not_active Withdrawn
- 1997-11-12 WO PCT/US1997/020448 patent/WO1998021171A1/en active IP Right Grant
- 1997-11-12 EP EP97948216A patent/EP0938461B1/en not_active Expired - Lifetime
- 1997-11-12 JP JP52271998A patent/JP3389251B2/en not_active Expired - Lifetime
- 1997-11-12 ES ES97948216T patent/ES2167798T3/en not_active Expired - Lifetime
-
1999
- 1999-12-20 US US09/467,869 patent/US6689924B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE69707490D1 (en) | 2001-11-22 |
| EP1104748A3 (en) | 2001-06-13 |
| CA2271341A1 (en) | 1998-05-22 |
| ES2167798T3 (en) | 2002-05-16 |
| EP0938461A1 (en) | 1999-09-01 |
| US6689924B1 (en) | 2004-02-10 |
| AU5432498A (en) | 1998-06-03 |
| DE69707490T2 (en) | 2002-05-23 |
| EP1104748A2 (en) | 2001-06-06 |
| KR100583800B1 (en) | 2006-05-26 |
| WO1998021171A1 (en) | 1998-05-22 |
| EP0938461B1 (en) | 2001-10-17 |
| JP3389251B2 (en) | 2003-03-24 |
| JP2001503771A (en) | 2001-03-21 |
| US6023004A (en) | 2000-02-08 |
| KR20000053190A (en) | 2000-08-25 |
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